JPS5855189B2 - Method for producing reactive monoazo dyes - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel method for producing reactive monoazo dyes.

More specifically, the present invention uses free acids of the following formula (1) (wherein, Phenylene group, which may be substituted, naphthylene E 6
or 0CONH represents the group 5O2CH=CH2 or the group -8O2CH2CH2Z.

Here, Z is a group that is eliminated with an alkali. R and R' each represent hydrogen or an alkyl group.

n represents an integer from 0 to 3) The present invention relates to a method for producing a reactive monoazo dye shown in the following.

Group -8O2CH=CH2 or its precursor group -8O2
It is well known that dyes with CH2CH20SO3H are used as reactive dyes for dyeing textile materials.

The present inventors have studied in detail the relationship between the structure and properties of this type of dye, and have found that the dye of formula (I) above has a high fixation rate and an extremely high fixation rate in dyeing various fiber materials, especially fibers containing hydroxyl groups. The object of the present invention is to provide a beautiful bluish-red dyed product with excellent wet fastness, and in particular, the dye has excellent chlorine fastness. It has been found that it is a useful dye.

In the reactive monoazo dye represented by the above formula (1), the group Z that is eliminated with an alkali is a hydroxyl group, a sulfuric acid ester group, a phosphoric acid ester group, a halogen atom, an alkyl or arylsulfonic acid ester group, an acyloxy group, an alkyl group. Alternatively, an aryl carbonate group, a carbamate group, an aryloxy group, a substituted or unsubstituted dialkylamino group, an N-alkyl-N-alkylsulfonylamino group, and a thiosulfate group are applicable.

In the formula (1), examples of X include chlorine, bromine, methoxy, ethoxy, n-propyloxy, n-butyloxy, 2-methoxyethyloxy, 2-ethoxyethyloxy, iso-propyloxy, phenoxy, sulfophenoxy, Examples include phenoxy groups and naphthyloxy groups containing methyl or methoxy groups as substitution valves.

The monoazo dye represented by the formula (I) can be produced by various methods, but for example, it can be produced industrially advantageously by the following method.

(A) An aminoazo dye of the following formula (II) (wherein R and n have the above meanings) and an aminoazo dye of the following formula (I)
amine of ID (wherein R', A1 and Y have the meanings given above) and optionally alcohols or phenols,
Obtained by condensation with cyanuric chloride in any order.

When Y in the obtained dye represents a group 5O2CH2CH20H, it can be converted into a sulfuric ester by the action of a sulfating agent if necessary.

In addition, in the obtained dye, Y is a group 5O2CH2CH2Z
, the group -8 is optionally treated with alkali.
It can also be changed to 02CH-CH2.

It is also possible to react dyes having a -8O2CH-CH2 group with thiosulfate to convert them into thiosulfate groups, or substituted or unsubstituted dialkylamines, N
-Alkyl-N-alkylsulfonylamines and phenols can also be added.

(b) Furthermore, the following formula (IV) (In the formula, R has the above meaning.

Xl represents a halogen atom, an alkoxy group, or an aryloxy group, and X2 represents a halogen atom or a group NR'-A-
Represents Y.

where R', A, Y have the above meanings) is coupled with the amine diazonium compound of the lower blade (in the formula, n has the above meanings), and when X2 represents a halogen atom; The dye of the formula (I) is obtained by reacting the amine of the above @ formula and, when Xl represents a halogen atom, optionally reacting with an alcohol or a phenol.

The aminoazo dye of formula (II) can be obtained by a conventional coupling method, and the coupling components used include, for example, 1-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-4 , 6-disulfonic acid, 1-amino-8-naphthol-3,5-disulfonic acid, 1-methylamino-8-naphthol-3,6-
These include disulfonic acid, 1-n-butylamino-8-naphthol-3.6- or 4,6-disulfonic acid, and -ethylamino-8-naphthol-3,6- or 4,6-disulfonic acid.

(Amines represented by formula IID include, for example, 3-aminophenyl-β-hydroxyethylsulfone, 4-aminophenyl-β-hydroxyethylsulfone, 2-aminophenyl-β-hydroxyethylsulfone, and alkyl, Compounds having alkoxy, chloro, and nitro substituents and their acidic sulfuric esters, 4-sulfo-3-aminophenyl-1-β-hydroxyethylsulfone and its acidic sulfuric esters, 4-carboxy-3-aminophenyl-1- β-Hydroxyethyl sulfone and its acidic sulfuric ester, 4-aminophenyl-vinyl sulfone, 3-aminophenyl-β-chloroethyl sulfone, 3-aminophenyl-β-acetoxyethyl sulfone, 3-aminophenyl-β-thiosulfone Artethyl sulfone, 3-aminophenyl-β-diethylaminoethyl sulfone, 3-amino-phenyl-β-dihydroxyethylaminoethyl sulfone, ethyl carbonate and carbamate ester of 3-aminophenyl-β-hydroxyethyl sulfone, 4-aminophenyl −
Aniline derivatives such as β-phenoxyethylsulfone and 4-β-hydroxyethylsulfonyl-1-naphthylamine, 5β-hydroxyethylsulfonyl-2-naphthylamine, 6-β-hydroxyethylsulfonyl-2-naphthylamine, 6-β-hydroxyethylsulfonyl −
Naphthylamines such as acidic sulfuric ester of 2-naphthylamine-8-sulfonic acid, 3-(4'-aminobenzoylamino)phenyl 1-β-hydroxyethylsulfone, and its phenyl nucleus with a dialkyl group, alkoxy group, or halogen atom substituted Compounds having as a group, 4-amino 4
'-β-hydroxyethylsulfonyl-diphenyl ether and its sulfuric ester, N-methyl 4-β-hydroxyethylsulfonylaniline, N-ethyl-4-β-
Examples include hydroxyethylsulfonylaniline.

The compound of formula (IV) can be obtained by condensing the coupling fraction and 2-substituted-4,6-cyhalotriazine used for the production of the aminoazo dye of formula (II) with optionally a mechanical amine. can be easily obtained by

Examples of amines of the formula (■) used as the diazo component include 2-naphthylamine-1-sulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 2-naphthylamine-1,6
-disulfonic acid, 2-naphthylamine-1,7-disulfonic acid, 2-naphthylamine-1,3,6-trisulfonic acid, 2-naphthylamine-1,3,7-trisulfonic acid, 2-naphthylamine-1,6, 8-1 lysulfonic acid,
2-naphthylamine-1,5,7-h lysulfonic acid, 2
-Naphthylamine-1,3,6-trisulfonic acid, 2-
Naphthylamine-1,3,6°7-titrasulfonic acid is used.

Suitable fiber materials to be dyed with the dye of the present invention include cellulose fibers such as wood thread and hemp, viscose human silk, viscose cotton, and paper, nitrogen-containing fibers such as polyvinyl alcohol fibers, wool, and polyamide.

For dyeing and printing, conventional dyeing methods, padding methods, and printing methods are widely applied.

Dyeing of cellulose fibers is carried out in a dye bath containing mirabilite or common salt in the presence of an acid binder at temperatures of 0 to 100°C, preferably 30 to 8°C.
This is done at 00C.

Padding dyeing involves applying an aqueous dye solution to the fibers and simultaneously or subsequently in the presence of an acid binder.
This is done by steaming or drying at 800C.

In addition, fibers that have been dyed in advance are mixed with 8 containing an acid binder.
It can also be carried out by immersion in a solution at 0 to 100°C.

It is also possible to treat the fibers only with an acid binder and then apply the dye.

Examples of the acid binder used here include caustic soda, soda carbonate, sodium bicarbonate, sodium triphosphate, and sodium silicate, which may be used alone or in combination as the case requires.

Printing is carried out using a one-phase method, in which a printing paste containing a dye and the above-mentioned acid binder is printed on a fiber and then steamed or dry-heated, or a printing paste containing a dye but not an acid binder is imprinted on a fiber, and then an acid binder is applied to the textile. Either of two-phase methods, such as treatment in a hot bath containing a sodium silicate aqueous solution, followed by hot or cold fixation, or imprinting with a glue containing an acid binder and steaming or drying. It can also be done by

At this time, it is also possible to perform discharge printing using an appropriate reducing agent.

Dyeing of natural or artificial polyamide fibers is carried out in an acid bath or a neutral bath, using an appropriate cationic activator, and after dyeing is started, the dyeing is neutralized with a mild alkali such as ammonia or hexamethylenetetramine. This results in good wet fastness.

The dyed product obtained by dyeing or printing cellulose fibers using the dye of the present invention has a beautiful bluish-red color and excellent light resistance and moisture resistance.

Furthermore, it is superior in that dyeings with markedly improved chlorine fastness can be obtained compared to similar dyes using benzene-based amines or naphthylamines other than 1-sulpo-2-naphthylamines as the diazo component.

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

In the text, parts represent parts by weight.

Example 1 18 parts of 2-methoxy-4,6-dichlorotriazine
-Amino-8-naphthol-3,6 disulfonic acid31.
Add to 150 parts of 9 parts of a neutral aqueous solution and add sodium carbonate (p) (stir at 40°C for 5 hours while maintaining the temperature between 6 and 7,
Add 25 parts of 4-methoxy-3-β-hydroxyethylsulfonylaniline and treat at 90-95°C for 5 hours.

Salt is added to salt out the precipitate, and the precipitate is filtered out and dried.

23 parts of dry matter (equivalent to 2 parts of sodium nitrite)
was added to 40 parts of concentrated sulfuric acid, discharged into a dissolving water drain, the crystals were separated in a furnace, the residue was dissolved in 50 parts of water, and 2-naphthylamine-
A solution of a diazonium salt obtained by a conventional method from 7.9 parts of 1,5-disulfonic acid is added, and coupling is carried out at pH 5 to 6.5.

Concentrate under reduced pressure and salt out by adding potassium chloride.

Separate the precipitate and dry it.

A brown powder was obtained. This thing has the structure of the following formula,
A cotton cloth was printed by a conventional method to obtain a vivid bluish-red print with high color yield, fastness to sunlight and washing, and excellent chlorine resistance.

To 40 parts of an aqueous solution containing 7.9 parts of 2-methoxy-4°6-
Add 4 parts of dichloro-1,3,5-triazine and add 40 to 5
React at 0'C.

During this time, adjust the pH to 6-7 with IJum.

Subsequently, 5 parts of 4-methoxy-3β-hydroxyethylsulforolaniline was added and heated to 95°C.

Salt out by adding potassium chloride and separate the precipitate from door to door.

Purify by recrystallization.

Dissolve 5 parts of the dry product in 20 parts of concentrated sulfuric acid and drain into water,
Add 20 parts of calcium carbonate and wash the solution thoroughly with water.
The washings are evaporated to dryness under reduced pressure.

The same dye as in Example 1 was obtained.

Example 3 18 parts of 2-methoxy-4,6-dichlorotriazine
-amino-8-naphthol-3,6-disulfonic acid 31
Add to 9 parts of a neutral aqueous solution and treat at 40°C for 5 hours at pH 6-7.

Add 35 parts of 4-methoxy 3-β-sulfatoethylsulfonylaniline and heat to 90°C.

Concentrate under reduced pressure, add potassium chloride and separate the precipitate.

The precipitate is dissolved in water, and an aqueous solution of a diazonium salt obtained from 18 parts of 2-naphthylamine-1,5-disulfonic acid by a conventional method is added thereto for coupling at pH 5 to 6.

Concentrate under reduced pressure and salt out by adding potassium chloride.

Example 4 2-naphthylamine-1, 2-naphthylamine-1, instead of 7.9 parts of 2-naphthylamine-1,5-disulfonic acid used in Example 1
A dye of the formula below was obtained using 10 parts of 5,7-trisulfonic acid but in the same manner as above. Met.

This product was resistant to sunlight and washing, and had excellent chlorine resistance.

Example 5 A solution of 18.5 parts of cyanuric chloride in 100 parts of acetone was added to 300 parts of water and 300 parts of crushed ice, and 2 parts of 2N hydrochloric acid were added to give 31.9 parts of ■-amino-8-naphthol 3.6-disulfonic acid. 150 parts of a neutral aqueous solution containing 50% of the mixture was added thereto, and the mixture was stirred at 5°C.

After the reaction was completed, 40 parts of crystalline sodium acetate was added, followed by 42 parts of 4-methoxy-3-β-sulfatoethylsulfonylaniline, and the mixture was stirred at 30°C.

Add a solution of diazonium salt obtained by a conventional method from 30.3 parts of 2-naphthylamine-1,5-disulfonic acid,
Coupling is carried out at pH 5-7.

Salt out by adding potassium chloride, separate the precipitate, and dry.

A reddish brown powder dye represented by the following formula was obtained.

The print obtained using the dye of the above formula had a hue similar to that of Example 4.

This product had good sunlight, washing and chlorine fastness.

Example 6 18 parts of 2-methoxy-4,6-dichlorotriazine used in Example 1 was replaced with 24.2 parts of 2-phenoxy-4°6-dichloro-1,3,5-triazine, and the other conditions were the same. A dye represented by the following formula was obtained.

A print similar to that of Example 5 was obtained by printing with 2 parts of the above dye.

Examples 7 to 26 The following table was prepared in the same manner as in Example 1 using the diazo component shown in the table below and the coupling component represented by the following formula (the types of each substituent Z1, Z2, and Z3 are shown in the table below). Each dye having the hue shown in the hue column was obtained.

Claims (1)

[Claims] 1 The following formula (wherein R represents hydrogen or an alkyl group, and n is O-
Represents an integer of 3. ), and aminoazo dyes of the following formula (wherein R' represents hydrogen or an alkyl group, and A is an alkoxy group, an alkyl group, a sulfonic acid group, a carboxyl group, or a phenylene group which may be substituted with a halogen) , naphthylene group, -fi\α-a or X=]cO
An amine represented by NTmo (=>, Y represents a group 5O2CH-CH2 or a group -8O2CH2CH2Z, where Z is a group that is eliminated with an alkali) and optionally alcohols or phenols, A free acid characterized in that it is condensed with cyanuric chloride in any order; A method for producing a reactive monoazo dye represented by (representing an oxy group). (In the formula, R represents hydrogen or an alkyl group; X1 represents a halogen atom, an alkoxy group, or an aryloxy group; , A represents an alkoxy group, an alkyl group, a sulfonic acid group, a carboxyl group or a phenylene group which may be substituted with a halogen, a naphthylene group, or OC, and Y represents a group 5O2CH-CH2 or a group -8O2CH2CH2Z. Here, Z is a group that is eliminated with an alkali.) A diazonium compound of an amine represented by the following formula (in the formula, n represents an integer of 0 to 3) is coupled to the compound represented by When it represents a halogen atom, an amine represented by the following formula % (in which R', A and Y have the above-mentioned meanings) is reacted, and when Xl represents a halogen atom, A free acid characterized by acting on alcohols or phenols according to the following formula (wherein R, R', A, Y and n have the above-mentioned meanings, and A method for producing a reactive monoazo dye represented by (representing an oxy group).